CN103288118A - Method for dissociating industrial by-product gypsum and crystallizing to grow calcium sulphate crystal whiskers - Google Patents
Method for dissociating industrial by-product gypsum and crystallizing to grow calcium sulphate crystal whiskers Download PDFInfo
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Abstract
The invention provides a method for dissociating industrial by-product gypsum and crystallizing to grow calcium sulphate crystal whiskers. The method comprises the following steps of: performing the pre-treatments of washing, dissociating, and filtering for removal of insoluble impurities on the cheap industrial by-product gypsum used as a raw materials, and dissociating the industrial by-product gypsum with a complex impurity content into pure solution containing calcium ions and sulphate ions; crystallizing the calcium ions and the sulphate ions in the conditions of certain acidity, reaction time, reaction temperature and crystal modifier; controlling crystal growth to prepare the high-grade calcium sulphate crystal whiskers. The prepared calcium sulphate crystal whiskers are 0.1-10 microns in diameter, 20-400 microns in length, 10-150 in length-diameter ratio, and greater than 99% in purity. By adopting the method provided by the invention, the current situation that lots of the industrial by-product gypsum is accumulated and cannot be effectively utilized can be improved; the process is stable and reliable; the products of calcium sulphate crystal whiskers are high in added value, and capable of being applied to the fields of plastic, rubber, papermaking, building and the like as fillers to act the effects of enhancement, heat insulation and flame retardance.
Description
Technical field:
The invention belongs to industry by-product gypsum recycling and functional additive technical field, particularly relate to utilize chemistry dissociate the purifying industry by-product gypsum and in liquid phase crystallization control growth calcium sulfate crystal whiskers, prepare the method for higher-grade calcium sulfate crystal whiskers.
Background technology:
Industry by-product gypsum mainly comprises the gypsum that calcium sulphate content such as fluorgypsum are higher, grade is lower of by-product in phosphogypsum that the desulfurated plaster that produces in flue gas desulfurization (FGD) process, phosphorus industry produces, the fluorine chemical, present method is namely at the recycling of desulfurated plaster, phosphogypsum and fluorgypsum, development of new technology and product.Because industry by-product gypsum is the by product in the industrial processes process, the restriction of raw material and processing condition causes its impurity component complexity, and water content is higher, and grain composition is relatively poor, and whiteness is lower, has caused obstacle for the recycling of industry by-product gypsum.Impurity in the industry by-product gypsum is complicated, and the ion of solubility is not only arranged, and some water-fast ash contents are also arranged, and causes whiteness low excessively, has reduced the mechanical property of gypsum, has had a strong impact on the application of industry by-product gypsum.Though the domestic plaster of paris aboundresources of China, but the Yangtze River Delta, area, Pearl River Delta plaster of paris scarcity of resources that industry is flourishing, and these regional industries are flourishing, and industry by-product gypsum output is abundant, provides real possibility for further utilizing industry by-product gypsum.Industry by-product gypsum can't be used effectively now at present, major part is piled up as solid waste, land occupation, contaminate environment, cause destruction to ecotope, simultaneously also caused burden to enterprise, how to have realized that the industry by-product gypsum recycling has become a problem demanding prompt solution.If the industry by-product gypsum resource utilization can be used, not only favourable to environment and society, also can increase economic efficiency for enterprise reduces the heavy burdens.
China's industry by-product gypsum generation is so big, utilization on a large scale not can't resolve root problem, makes a general survey of the Application Areas of domestic and international industry by-product gypsum, just as can be seen, building materials industry and building material goods industry are to use its most extensive, that consumption is maximum field.Also do not carry out large-scale high value added utilization in the method for comprehensive utilization of industry by-product gypsum now, utilize the industry by-product gypsum resource utilization to prepare the method for calcium sulfate crystal whiskers, for the industry by-product gypsum high value added utilization provides the recycling approach, the potential Application Areas of calcium sulfate crystal whiskers is extensive, and effective popularization of present technique can realize the extensive recycling of industry by-product gypsum.
Summary of the invention:
The objective of the invention is in order to realize being prepared by industry by-product gypsum the calcium sulfate crystal whiskers product of high added value, industry by-product gypsum is as a kind of industrial by-products, because its raw materials for production and preparation technology's restriction contains the various impurity component of kind in the industry by-product gypsum.Adopt technological line provided by the present invention, can realize that the purifying of different sorts industry by-product gypsum reaches with it as the feedstock production calcium sulfate crystal whiskers.
Technical scheme of the present invention is:
The method of industry by-product gypsum disassociation and crystalline growth calcium sulfate crystal whiskers, it is characterized in that, it is to utilize industry by-product gypsum, industry by-product gypsum is dissociated, and then will dissociate resulting ionic calcium soln and the mixing of sulfate radical solution, by crystallization reaction control, make it be grown to higher-grade calcium sulfate crystal whiskers product then.
The method of industry by-product gypsum disassociation and crystalline growth calcium sulfate crystal whiskers, it may further comprise the steps:
1) pre-treatment: industry by-product gypsum is removed soluble impurity through washing, filtration;
2) disassociation:
2.1) industry by-product gypsum and soluble carbon hydrochlorate are reacted under agitation condition, make it be converted into precipitation of calcium carbonate and sulfate radical solution fully, by filtering solid-liquid separation, obtain calcium carbonate and sulfate radical solution;
2.2) with step 2.1) the resulting calcium carbonate of precipitation is decomposed into ionic calcium soln with mineral acid, and by removing by filter insoluble impurities wherein;
3) resulting ionic calcium soln and sulfate radical solution mix with mineral acid and crystal modifier preparation calcium sulfate crystal whiskers: with step 2), the concentration that the concentration of guaranteeing ionic calcium soln and sulfate radical solution is 0.1～1.0mol/l, mineral acid is 0.1～1.0mol/l, be to react 1～4 hour under 105～112 conditions of spending in temperature of reaction then, obtain preliminary calcium sulfate crystal whiskers by crystallization reaction control growth;
4) aftertreatment: resulting preliminary calcium sulfate crystal whiskers is namely got the calcium sulfate crystal whiskers finished product through washing, filtration, drying treatment again.
Described industry by-product gypsum comprises phosphogypsum, desulfurated plaster or fluorgypsum etc.Present method is applicable to multiple industry by-product gypsum.
Described step 2.1) in, described soluble carbon hydrochlorate is yellow soda ash, and described sulfate radical solution is metabisulfite solution.The soluble carbon hydrochlorate all can reach corresponding effect, and metabisulfite solution is better.
Described step 2.2) in, with step 2.1) to decompose the mineral acid that adopts be hydrochloric acid or nitric acid to the resulting calcium carbonate of precipitation.
Corresponding to step 2.1) to decompose the mineral acid that adopts be hydrochloric acid or nitric acid to the resulting calcium carbonate of precipitation, described ionic calcium soln is calcium chloride or nitrocalcite.
In the described step 3), with step 2) two kinds of solution of disassociation resulting ionic calcium soln and sulfate radical solution mix, crystallization reaction control is grown to calcium sulfate crystal whiskers reaction conditions is as follows: the reaction times is 1～4 hour, temperature of reaction is 105～112 degree, inorganic acid concentration is 0.1～1.0mol/l, the concentration of ionic calcium soln and sulfate radical solution is 0.1～1.0mol/l, and the crystal modifier that crystallization reaction adopts is oleic acid, silane coupling agent or magnesium chloride.Wherein, described mineral acid is step 2) leave or interpolation afterwards its corresponding step 2) be hydrochloric acid or nitric acid.The concentration of control mixed solution and the chief component that correlated condition is present method.
Be hydrochloric acid with the mineral acid, the soluble carbon hydrochlorate is that yellow soda ash is that example is introduced the process that present method prepares calcium sulfate crystal whiskers.A. at first carry out the pre-treatment of industry by-product gypsum, through washing, remove by filter the soluble impurity in the industry by-product gypsum.Industry by-product gypsum and yellow soda ash are reacted under agitation condition, make it be converted into precipitation of calcium carbonate and metabisulfite solution fully, by filtering both are separated.Calcium carbonate is decomposed into the solution that contains calcium ion with mineral acid, removes by filter the insoluble impurities in the industry by-product gypsum.B. the resulting solution that contains calcium ion and sulfate ion is mixed, crystallization reaction control is grown to calcium sulfate crystal whiskers, its reaction conditions is as follows: the reaction times is that 1～4 hour, temperature of reaction are that 105～112 degree, concentration of hydrochloric acid are that the crystal modifier that the concentration (concentration of calcium ion and sulfate ion) of 0.1～1.0mol/l, calcium chloride and sodium sulfate is 0.1～1.0mol/l, employing is oleic acid, silane coupling agent, magnesium chloride.Namely get the calcium sulfate crystal whiskers finished product through washing, filtration, drying treatment again.
The present invention is based on industry by-product gypsum main component calcium sulfate, makes its disassociation, purifying, recrystallize prepare calcium sulfate crystal whiskers.Because calcium sulfate is sl. sol., its solubleness is greater than calcium carbonate, in aqueous sodium carbonate, can realize easily by the conversion process of calcium sulfate to calcium carbonate, thereby from industry by-product gypsum, dissociate calcium ion and sulfate ion, the metabisulfite solution that obtains is standby, adopt mineral acid calcium carbonate can be decomposed and be the solution of calcium ion, process can be removed the insoluble solid impurities that contains in the industry by-product gypsum after filtration again, thereby realizes the purifying of industry by-product gypsum.Contain sulfate ion solution and ionic calcium soln mixes under given conditions, crystalline growth with the front is resulting, namely control liquid growth, namely obtain the calcium sulfate crystal whiskers product.
The whole process reaction of the present invention is very fast, the efficient height, can only be about 40% with whiteness, calcium sulphate content is 70～90% industry by-product gypsum, prepare lily high purity calcium sulfate crystal whiskers product (purity can reach more than 98%), also can prepare high-grade anhydrous calcium sulfate whisker by high-temperature calcination, be conducive to the product development of recycling and the calcium sulfate crystal whiskers of industry by-product gypsum.
Description of drawings:
Fig. 1: industry by-product gypsum disassociation and crystallization control growth calcium sulfate crystal whiskers schema;
Fig. 2: the calcium sulfate crystal whiskers stereoscan photograph that the present invention is prepared;
Fig. 3: the calcium sulfate crystal whiskers XRD figure that the present invention is prepared.
Embodiment:
Embodiment 1:
Referring to Fig. 1, the method for preparing the higher-grade calcium sulfate crystal whiskers provided by the invention is characterized in that, it is that industry by-product gypsum is dissociated, and then will dissociate resulting ionic calcium soln and the mixing of sulfate radical solution, by crystallization reaction control, make it be grown to higher-grade calcium sulfate crystal whiskers product then.
It may further comprise the steps:
1) pre-treatment: industry by-product gypsum is removed soluble impurity through washing, filtration;
2) disassociation: 2.1) industry by-product gypsum and soluble carbon hydrochlorate are reacted under agitation condition, make it be converted into precipitation of calcium carbonate and sulfate radical solution fully, by filtering solid-liquid separation, obtain calcium carbonate and sulfate radical solution; 2.2) with step 2.1) the resulting calcium carbonate of precipitation is decomposed into ionic calcium soln with mineral acid, and by removing by filter insoluble impurities wherein;
3) resulting ionic calcium soln and sulfate radical solution mix preparation calcium sulfate crystal whiskers: with step 2), add mineral acid and crystal modifier again, the concentration that the concentration of guaranteeing ionic calcium soln and sulfate radical solution is 0.1～1.0mol/l, mineral acid is 0.1～1.0mol/l, be to react 1～4 hour under 105～112 conditions of spending in temperature of reaction then, obtain preliminary calcium sulfate crystal whiskers by crystallization reaction control growth;
4) aftertreatment: the resulting preliminary calcium sulfate crystal whiskers of step 3) can be obtained the calcium sulfate crystal whiskers finished product through washing, filtration, drying treatment again.
Described industry by-product gypsum comprises phosphogypsum, desulfurated plaster or fluorgypsum etc.Present method is applicable to multiple industry by-product gypsum.
In the described step 2.1), described soluble carbon hydrochlorate is yellow soda ash, described sulfate radical solution is metabisulfite solution.The soluble carbon hydrochlorate is received lodgers and is reached corresponding effect, and metabisulfite solution is better.
Described step 2.2) in, with step 2.1) to decompose the mineral acid that adopts be hydrochloric acid or nitric acid to the resulting calcium carbonate of precipitation.Corresponding to step 2.1) to decompose the mineral acid that adopts be hydrochloric acid or nitric acid to the resulting calcium carbonate of precipitation, described ionic calcium soln is calcium chloride or nitrocalcite.
Mineral acid in the described step 3) is hydrochloric acid or nitric acid, and crystal modifier is oleic acid, silane coupling agent or magnesium chloride.
Embodiment 2:
Referring to Fig. 1, the method for industry by-product gypsum disassociation and crystalline growth calcium sulfate crystal whiskers, it may further comprise the steps:
1) pre-treatment: industry by-product gypsum is removed soluble impurity through washing, filtration;
2) disassociation: 2.1) with industry by-product gypsum and yellow soda ash in reaction 2 hours in 50 degree waters bath with thermostatic control under the agitation condition, make it be converted into precipitation of calcium carbonate and metabisulfite solution fully, by filtering both separation; 2.2) with step 2.1) and the precipitation resulting calcium carbonate be decomposed into calcium chloride solution with hydrochloric acid, by removing by filter the insoluble impurities in the desulfurated plaster;
3) resulting calcium chloride solution and metabisulfite solution mix preparation calcium sulfate crystal whiskers: with step 2), add hydrochloric acid and oleic acid again, the concentration that the concentration of guaranteeing calcium chloride and sodium sulfate is 0.1mol/l, hydrochloric acid is 0.1mol/l, be to react 1 hour under 105 conditions of spending in temperature of reaction then, obtain preliminary calcium sulfate crystal whiskers by crystallization reaction control growth;
4) aftertreatment: the resulting preliminary calcium sulfate crystal whiskers of step 3) can be obtained the calcium sulfate crystal whiskers finished product through washing, filtration, drying treatment again.
Industry by-product gypsum in the described step 1) comprises phosphogypsum, desulfurated plaster or fluorgypsum etc.Its washing, filtration can be done accommodation by the particular case of industry by-product gypsum, remove soluble impurity to satisfy.
Described step 2.1) in, industry by-product gypsum and yellow soda ash were reacted 2 hours under agitation condition with in the 50 degree waters bath with thermostatic control.Wherein temperature and time can be done accommodation, makes it be converted into precipitation of calcium carbonate and metabisulfite solution fully to reach.
In the described step 3), add hydrochloric acid and oleic acid (crystal modifier), available nitric acid replaces hydrochloric acid, and available silane coupling agent or magnesium chloride substitute oleic acid.
Embodiment 3:
Referring to Fig. 1, the method for industry by-product gypsum disassociation and crystalline growth calcium sulfate crystal whiskers, it may further comprise the steps:
1) pre-treatment: industry by-product gypsum is removed soluble impurity through washing, filtration;
2) disassociation: 2.1) with industry by-product gypsum and yellow soda ash in reaction 2 hours in 50 degree waters bath with thermostatic control under the agitation condition, make it be converted into precipitation of calcium carbonate and metabisulfite solution fully, by filtering both separation; 2.2) with step 2.1) and the precipitation resulting calcium carbonate be decomposed into ca nitrate soln with nitric acid, remove by filter the insoluble impurities in the desulfurated plaster;
3) resulting ca nitrate soln and metabisulfite solution mix preparation calcium sulfate crystal whiskers: with step 2), add nitric acid and oleic acid again, the concentration that the concentration of guaranteeing nitrocalcite and sodium sulfate is 0.1mol/l, nitric acid is 0.1mol/l, be to react 1 hour under 105 conditions of spending in temperature of reaction then, obtain preliminary calcium sulfate crystal whiskers by crystallization reaction control growth;
4) aftertreatment: the resulting preliminary calcium sulfate crystal whiskers of step 3) can be obtained the calcium sulfate crystal whiskers finished product through washing, filtration, drying treatment again.
Industry by-product gypsum in the described step 1) comprises phosphogypsum, desulfurated plaster or fluorgypsum etc.Its washing, filtration can be done accommodation by the particular case of industry by-product gypsum, remove soluble impurity to satisfy.
Described step 2.1) in, industry by-product gypsum and yellow soda ash were reacted 2 hours under agitation condition with in the 50 degree waters bath with thermostatic control.Wherein temperature and time can be done accommodation, makes it be converted into precipitation of calcium carbonate and metabisulfite solution fully to reach.
In the described step 3), add nitric acid acid and oleic acid (crystal modifier), acceptable salts acid substitution nitric acid, available silane coupling agent or magnesium chloride substitute oleic acid.
Embodiment 4:
Referring to Fig. 1, the method for industry by-product gypsum disassociation and crystalline growth calcium sulfate crystal whiskers, it may further comprise the steps:
1) pre-treatment: industry by-product gypsum is removed soluble impurity through washing, filtration;
2) disassociation: 2.1) with industry by-product gypsum and yellow soda ash in reaction 2 hours in 50 degree waters bath with thermostatic control under the agitation condition, make it be converted into precipitation of calcium carbonate and metabisulfite solution fully, by filtering both separation; 2.2) with step 2.1) and the precipitation resulting calcium carbonate be decomposed into calcium chloride solution with hydrochloric acid, by removing by filter the insoluble impurities in the desulfurated plaster;
3) resulting calcium chloride solution and metabisulfite solution mix preparation calcium sulfate crystal whiskers: with step 2), add hydrochloric acid and oleic acid again, the concentration that the concentration of guaranteeing calcium chloride and sodium sulfate is 0.5mol/l, hydrochloric acid is 0.2mol/l, be to react 2 hours under 112 conditions of spending in temperature of reaction then, obtain preliminary calcium sulfate crystal whiskers by crystallization reaction control growth;
4) aftertreatment: the resulting preliminary calcium sulfate crystal whiskers of step 3) can be obtained the calcium sulfate crystal whiskers finished product through washing, filtration, drying treatment again.
Industry by-product gypsum in the described step 1) comprises phosphogypsum, desulfurated plaster or fluorgypsum etc.Its washing, filtration can be done accommodation by the particular case of industry by-product gypsum, remove soluble impurity to satisfy.
Described step 2.1) in, industry by-product gypsum and yellow soda ash were reacted 2 hours under agitation condition with in the 50 degree waters bath with thermostatic control.Wherein temperature and time can be done accommodation, makes it be converted into precipitation of calcium carbonate and metabisulfite solution fully to reach.
In the described step 3), add hydrochloric acid and oleic acid (crystal modifier), available nitric acid replaces hydrochloric acid, and available silane coupling agent or magnesium chloride substitute oleic acid.
Embodiment 5:
Referring to Fig. 1, the method for industry by-product gypsum disassociation and crystalline growth calcium sulfate crystal whiskers, it may further comprise the steps:
1) pre-treatment: industry by-product gypsum is removed soluble impurity through washing, filtration;
2) disassociation: 2.1) with industry by-product gypsum and yellow soda ash in reaction 2 hours in 50 degree waters bath with thermostatic control under the agitation condition, make it be converted into precipitation of calcium carbonate and metabisulfite solution fully, by filtering both separation; 2.2) with step 2.1) and the precipitation resulting calcium carbonate be decomposed into ca nitrate soln with nitric acid, remove by filter the insoluble impurities in the desulfurated plaster;
3) resulting ca nitrate soln and metabisulfite solution mix preparation calcium sulfate crystal whiskers: with step 2), add nitric acid and oleic acid again, the concentration that the concentration of guaranteeing nitrocalcite and sodium sulfate is 0.5mol/l, nitric acid is 0.2mol/l, be to react 2 hours under 112 conditions of spending in temperature of reaction then, by crystallization reaction control growth, obtain preliminary calcium sulfate crystal whiskers;
4) aftertreatment: the resulting preliminary calcium sulfate crystal whiskers of step 3) can be obtained the calcium sulfate crystal whiskers finished product through washing, filtration, drying treatment again.
Industry by-product gypsum in the described step 1) comprises phosphogypsum, desulfurated plaster or fluorgypsum etc.Its washing, filtration can be done accommodation by the particular case of industry by-product gypsum, remove soluble impurity to satisfy.
Described step 2.1) in, industry by-product gypsum and yellow soda ash were reacted 2 hours under agitation condition with in the 50 degree waters bath with thermostatic control.Wherein temperature and time can be done accommodation, makes it be converted into precipitation of calcium carbonate and metabisulfite solution fully to reach.
In the described step 3), add nitric acid acid and oleic acid (crystal modifier), acceptable salts acid substitution nitric acid, available silane coupling agent or magnesium chloride substitute oleic acid.
Embodiment 6:
Referring to Fig. 1, the method for industry by-product gypsum disassociation and crystalline growth calcium sulfate crystal whiskers, it may further comprise the steps:
1) pre-treatment: industry by-product gypsum is removed soluble impurity through washing, filtration;
2) disassociation: 2.1) with industry by-product gypsum and yellow soda ash in reaction 2 hours in 50 degree waters bath with thermostatic control under the agitation condition, make it be converted into precipitation of calcium carbonate and metabisulfite solution fully, by filtering both separation; 2.2) with step 2.1) and the precipitation resulting calcium carbonate be decomposed into calcium chloride solution with hydrochloric acid, by removing by filter the insoluble impurities in the desulfurated plaster;
3) resulting calcium chloride solution and metabisulfite solution mix preparation calcium sulfate crystal whiskers: with step 2), add hydrochloric acid and oleic acid again, the concentration that the concentration of guaranteeing calcium chloride and sodium sulfate is 1.0mol/l, hydrochloric acid is 1.0mol/l, be to react 4 hours under 112 conditions of spending in temperature of reaction then, crystallization reaction control is grown to preliminary calcium sulfate crystal whiskers;
4) aftertreatment: the resulting preliminary calcium sulfate crystal whiskers of step 3) can be obtained the calcium sulfate crystal whiskers finished product through washing, filtration, drying treatment again.
Industry by-product gypsum in the described step 1) comprises phosphogypsum, desulfurated plaster or fluorgypsum etc.Its washing, filtration can be done accommodation by the particular case of industry by-product gypsum, remove soluble impurity to satisfy.
Described step 2.1) in, industry by-product gypsum and yellow soda ash were reacted 2 hours under agitation condition with in the 50 degree waters bath with thermostatic control.Wherein temperature and time can be done accommodation, makes it be converted into precipitation of calcium carbonate and metabisulfite solution fully to reach.
In the described step 3), add hydrochloric acid and oleic acid (crystal modifier), available nitric acid replaces hydrochloric acid, and available silane coupling agent or magnesium chloride substitute oleic acid.
Embodiment 7:
Referring to Fig. 1, the method for industry by-product gypsum disassociation and crystalline growth calcium sulfate crystal whiskers, it may further comprise the steps:
1) pre-treatment: industry by-product gypsum is removed soluble impurity through washing, filtration;
2) disassociation: 2.1) with industry by-product gypsum and yellow soda ash in reaction 2 hours in 50 degree waters bath with thermostatic control under the agitation condition, make it be converted into precipitation of calcium carbonate and metabisulfite solution fully, by filtering both separation; 2.2) with step 2.1) and the precipitation resulting calcium carbonate be decomposed into ca nitrate soln with nitric acid, remove by filter the insoluble impurities in the desulfurated plaster;
3) resulting ca nitrate soln and metabisulfite solution mix preparation calcium sulfate crystal whiskers: with step 2), add nitric acid and oleic acid again, the concentration that the concentration of guaranteeing nitrocalcite and sodium sulfate is 1.0mol/l, nitric acid is 1.0mol/l, be to react 4 hours under 112 conditions of spending in temperature of reaction then, crystallization reaction control is grown to preliminary calcium sulfate crystal whiskers;
4) aftertreatment: the resulting preliminary calcium sulfate crystal whiskers of step 3) can be obtained the calcium sulfate crystal whiskers finished product through washing, filtration, drying treatment again.
Industry by-product gypsum in the described step 1) comprises phosphogypsum, desulfurated plaster or fluorgypsum etc.Its washing, filtration can be done accommodation by the particular case of industry by-product gypsum, remove soluble impurity to satisfy.
Described step 2.1) in, industry by-product gypsum and yellow soda ash were reacted 2 hours under agitation condition with in the 50 degree waters bath with thermostatic control.Wherein temperature and time can be done accommodation, makes it be converted into precipitation of calcium carbonate and metabisulfite solution fully to reach.
In the described step 3), add nitric acid acid and oleic acid (crystal modifier), acceptable salts acid substitution nitric acid, available silane coupling agent or magnesium chloride substitute oleic acid.
Fig. 2 is the prepared calcium sulfate crystal whiskers stereoscan photograph of the embodiment of the invention; Fig. 3 is the prepared calcium sulfate crystal whiskers XRD figure of the embodiment of the invention.Prepared calcium sulfate crystal whiskers diameter is 0.1 to 10 micron, and length is 20 to 400 microns, and length-to-diameter ratio is that purity is higher than 99% between 10 to 150.Whole process reaction is very fast, the efficient height, can only be about 40% with whiteness, calcium sulphate content is that 70～90% industry by-product gypsum prepares lily high purity calcium sulfate crystal whiskers product, also can prepare anhydrous calcium sulfate whisker by high-temperature calcination, be conducive to the product development of recycling and the calcium sulfate crystal whiskers of industry by-product gypsum.
The above only is preferable possible embodiments of the present invention, is not in order to limit to claim of the present invention, so the equivalent structure that all utilizations specification sheets of the present invention and accompanying drawing content are done changes, all to be included in protection scope of the present invention.
Claims (8)
1. the method for industry by-product gypsum disassociation and crystalline growth calcium sulfate crystal whiskers, it is characterized in that at first with the industry by-product gypsum disassociation, will dissociate then resulting ionic calcium soln and sulfate radical solution mix, by crystallization reaction control, make it be grown to high-grade calcium sulfate crystal whiskers then.
2. according to the method for preparing the higher-grade calcium sulfate crystal whiskers described in the claim 1, it is characterized in that it specifically comprises the steps:
1) pre-treatment: with industry by-product gypsum washing, filtration, remove soluble impurity;
2) disassociation:
2.1) industry by-product gypsum and soluble carbon hydrochlorate are reacted under agitation condition, make it be converted into precipitation of calcium carbonate and sulfate radical solution fully, by filtering solid-liquid separation, obtain calcium carbonate and sulfate radical solution;
2.2) with step 2.1) the resulting calcium carbonate of precipitation is decomposed into ionic calcium soln with mineral acid, and by removing by filter insoluble impurities wherein;
3) resulting ionic calcium soln and sulfate radical solution mix with mineral acid and crystal modifier crystallization reaction control: with step 2), the concentration that the concentration of guaranteeing ionic calcium soln and sulfate radical solution is 0.1～1.0mol/l, mineral acid is 0.1～1.0mol/l, be to react 1～4 hour under 105～112 conditions of spending in temperature of reaction then, crystallization reaction control is grown to preliminary calcium sulfate crystal whiskers;
4) aftertreatment: resulting preliminary calcium sulfate crystal whiskers is namely got the calcium sulfate crystal whiskers finished product through washing, filtration, drying treatment again.
3. according to the method for preparing the higher-grade calcium sulfate crystal whiskers described in claim 1 or 2, it is characterized in that: described industry by-product gypsum is phosphogypsum, desulfurated plaster or fluorgypsum.
4. according to the method for preparing the higher-grade calcium sulfate crystal whiskers described in the claim 2, it is characterized in that: in the described step 2.1), described soluble carbon hydrochlorate is yellow soda ash, described sulfate radical solution is metabisulfite solution.
5. according to the method for preparing the higher-grade calcium sulfate crystal whiskers described in the claim 2, it is characterized in that: described step 2.2), with step 2.1) to decompose the mineral acid that adopts be hydrochloric acid or nitric acid to the resulting calcium carbonate of precipitation.
6. according to the method for preparing the higher-grade calcium sulfate crystal whiskers described in the claim 5, it is characterized in that: corresponding to step 2.1) to decompose the mineral acid that adopts be hydrochloric acid or nitric acid to the resulting calcium carbonate of precipitation, described ionic calcium soln is calcium chloride or nitrocalcite.
7. according to the method for preparing the higher-grade calcium sulfate crystal whiskers described in the claim 2, it is characterized in that: the crystal modifier in the described step 3) is oleic acid, silane coupling agent or magnesium chloride.
8. according to the method for preparing the higher-grade calcium sulfate crystal whiskers described in the claim 2, it is characterized in that: described step 4) is further comprising the steps of: with the resulting preliminary calcium sulfate crystal whiskers high-temperature calcination of crystallization reaction control growth, be prepared into anhydrous calcium sulfate whisker.
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| CN106430273A (en) * | 2016-09-30 | 2017-02-22 | 四川什邡市星天丰科技有限公司 | Method for preparing anhydrous calcium sulfate filler by using phosphogypsum |
| CN108796612A (en) * | 2018-06-06 | 2018-11-13 | 湖北三宁化工股份有限公司 | A kind of method of ardealite Cycle-decomposition Sulphuric acid calcium pyroborate coproduction of ammonia sulfate |
| CN110528060A (en) * | 2019-08-28 | 2019-12-03 | 三明学院 | The method and calcium sulfate crystal whiskers of fluorgypsum slag growth calcium sulfate crystal whiskers |
| CN111072054A (en) * | 2019-12-31 | 2020-04-28 | 安徽六国化工股份有限公司 | Preparation of high-purity gypsum powder and byproduct NH from phosphogypsum4Cl process |
| CN111778560A (en) * | 2019-04-04 | 2020-10-16 | 西南科技大学 | Controllable preparation method of nano anhydrous calcium sulfate fiber |
| CN112850772A (en) * | 2021-01-29 | 2021-05-28 | 中蓝长化工程科技有限公司 | Method for preparing calcium sulfate by using calcium-containing waste liquor of fluorite ore |
| CN113480209A (en) * | 2021-07-16 | 2021-10-08 | 昆明理工大学 | Method for preparing high-strength building gypsum by dry method |
| CN115259200A (en) * | 2022-07-26 | 2022-11-01 | 一夫科技股份有限公司 | Simple and efficient method for preparing ultrafine gypsum |
| CN115504695A (en) * | 2022-09-06 | 2022-12-23 | 宜昌邦普循环科技有限公司 | Phosphogypsum recycling method |
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| CN104495774A (en) * | 2014-12-08 | 2015-04-08 | 宜昌市三峡天润纳米材料工程技术研究中心有限公司 | Method for co-production of nanometer hydroxyapatite and calcium sulfate whisker from phosphogypsum |
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| CN105220233A (en) * | 2015-10-22 | 2016-01-06 | 昆明理工大学 | A kind of take phosphogypsum as the method that high-purity sulphuric acid calcium pyroborate prepared by raw material |
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| CN110528060A (en) * | 2019-08-28 | 2019-12-03 | 三明学院 | The method and calcium sulfate crystal whiskers of fluorgypsum slag growth calcium sulfate crystal whiskers |
| CN111072054A (en) * | 2019-12-31 | 2020-04-28 | 安徽六国化工股份有限公司 | Preparation of high-purity gypsum powder and byproduct NH from phosphogypsum4Cl process |
| CN112850772A (en) * | 2021-01-29 | 2021-05-28 | 中蓝长化工程科技有限公司 | Method for preparing calcium sulfate by using calcium-containing waste liquor of fluorite ore |
| CN113480209A (en) * | 2021-07-16 | 2021-10-08 | 昆明理工大学 | Method for preparing high-strength building gypsum by dry method |
| CN115259200A (en) * | 2022-07-26 | 2022-11-01 | 一夫科技股份有限公司 | Simple and efficient method for preparing ultrafine gypsum |
| CN115259200B (en) * | 2022-07-26 | 2023-11-07 | 一夫科技股份有限公司 | Simple and efficient method for preparing superfine gypsum |
| CN115504695A (en) * | 2022-09-06 | 2022-12-23 | 宜昌邦普循环科技有限公司 | Phosphogypsum recycling method |
| CN115504695B (en) * | 2022-09-06 | 2023-12-12 | 宜昌邦普循环科技有限公司 | Phosphogypsum recycling method |
| WO2024051103A1 (en) * | 2022-09-06 | 2024-03-14 | 宜昌邦普循环科技有限公司 | Phosphogypsum recovery method |
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Application publication date: 20130911 |